Alkylated aromatic compositions, zeolite catalyst compositions and processes for making the same

ABSTRACT

The present invention is directed to novel alkylated aromatic compositions, zeolite catalyst compositions and processes for making the same. The catalyst compositions comprise zeolite Y and mordenite zeolite having a controlled macropore structure. The present invention is also directed to the preparation of the catalyst compositions and their use in the preparation of novel alkylated aromatic compositions. The catalyst compositions of the present invention exhibit reduced deactivation rates during the alkylation process, thereby increasing the life of the catalysts.

This application is a Divisional of application Ser. No. 10/799,907,filed Mar. 12, 2004 now U.S. Pat. No. 6,977,319.

FIELD OF THE INVENTION

The present invention is directed to novel alkylated aromaticcompositions, zeolite catalyst compositions and processes for making thesame. The catalyst compositions comprise zeolite Y and mordenite zeolitehaving a controlled macropore structure. The present invention is alsodirected to the preparation of the catalyst compositions and their usein the preparation of novel alkylated aromatic compositions. Thecatalyst compositions of the present invention exhibit reduceddeactivation rates during the alkylation process, thereby increasing thelife of the catalysts.

BACKGROUND OF THE INVENTION

It is well known to catalyze the alkylation of aromatics with a varietyof Lewis or Bronsted acid catalysts. Typical commercial catalystsinclude phosphoric acid/kieselguhr, aluminum halides, boron trifluoride,antimony chloride, stannic chloride, zinc chloride, onium poly(hydrogenfluoride), and hydrogen fluoride. Alkylation with lower molecular weightolefins, such as propylene, can be carried out in the liquid or vaporphase. For alkylations with higher olefins, such as C₁₆ olefins, thealkylations are done in the liquid phase, usually in the presence ofhydrogen fluoride. Alkylation of benzene with higher olefins isespecially difficult, and requires hydrogen fluoride treatment. However,hydrogen fluoride is not environmentally attractive.

The use of the above listed acids is extremely corrosive, thus requiringspecial handling and equipment. Also, the use of these acids mightinvolve environmental problems. Another problem is that the use of theseacids can give less than desirable control on the precise chemicalcomposition of the product produced. Thus, it is preferable to use asafer, simpler catalyst, preferably in solid state. This simpler processwould result in less capital investment, which would result in a lessexpensive product.

Solid crystalline aluminosilicate zeolite catalysts have been known tobe effective for the alkylation of aromatics with olefins. Zeoliticmaterials which are useful as catalysts are usually inorganiccrystalline materials that possess uniform pores with diameters inmicropore range that is less than 20 angstroms. Zeolites occur naturallyand may also be prepared synthetically. Synthetic zeolites include, forexample, zeolites A, X, Y, L and omega. It is also possible to generatemetaloaluminophosphates and metalosilicophosphates. Other materials,such as boron, gallium, iron or germanium, may also be used to replacethe aluminum or silicon in the framework structure.

These zeolite catalyst materials are commercially available as finecrystalline powders for further modification to enhance their catalyticproperties for particular applications. Processes for the furthermodification to enhance catalytic properties of the zeolite catalystsare well known in the art, such as forming the zeolite catalysts intoshaped particles, exchanging the cations in the catalyst matrix, etc.

Forming zeolite powders into shaped particles may be accomplished byforming a gel or paste of the catalyst powder with the addition of asuitable binder material such as a clay, an inorganic compound, or anorganic compound and then extruding the gel or paste into the desiredform. Zeolite powders may also be formed into particles without the useof a binder. Typical catalyst particles include extrudates whose crosssections are circular or embrace a plurality of arcuate lobes extendingoutwardly from the central portion of the catalyst particles.

One problem with catalyst particles used in fixed bed reactors iscatalyst deactivation. In most hydrocarbon conversion processes,including alkylation, the primary catalyst deactivation is caused bycoke formation. This catalyst deactivation is a serious problem in theuse of zeolite catalysts for alkylation reactions. This deactivationproblem is well known in the art and it is well understood that thedeactivation mechanism can involve polymerization of the olefin intolarge molecular species that cannot diffuse out of the pores containingthe active sites in the zeolitic material.

The use of zeolite catalysts for preparation of alkyl aromatics istypically conducted by the catalytic alkylation of aromatic hydrocarbonswith normal alpha olefins or branched-chain olefins, and optionally apromotor. The alkylated aromatic hydrocarbons can be converted intocorresponding sulfonic acids which can be further converted intoalkylated aromatic sulfonates.

A number of patents have discussed processes for the preparation ofzeolite catalysts and the further shaping and forming of the catalystparticles and extrudates with and without the use of binders. There arealso a number of patents disclosing the use of zeolite catalysts foralkylation of aromatic hydrocarbons.

U.S. Pat. No. 3,094,383 discloses the preparation of synthetic zeolitematerials which upon hydration yield a sorbent of controlled effectivepore diameter and in which the sorbent and its zeolite precursor areprovided directly in the form of an aggregate.

U.S. Pat. No. 3,130,007 discloses the method of preparing sodium zeoliteY with silica to alumina ratios ranging from greater than 3 to about3.9.

U.S. Pat. No. 3,119,660 discloses a process for making massive bodies orshapes of crystalline zeolites. The patent also discloses methods forthe identification of the catalyst materials using X-ray powderdiffraction patterns in conjunction with chemical analyses.

U.S. Pat. No. 3,288,716 discloses that the high “heavy content” of thealkylated aromatic product can be controlled during the alkylation stepand has advantages over distilling the alkylated aromatic product toobtain the desired molecular weight.

U.S. Pat. Nos. 3,641,177 and 3,929,672 disclose the technique to removesodium or other alkali metal ions from zeolite catalysts. The '177patent also discloses that such removal of the sodium or other alkalimetal ions activates the zeolite catalysts for the alkylation ofaromatic hydrocarbons with olefins by liquid phase reaction.

U.S. Pat. Nos. 3,764,533, 4,259,193 and 5,112,506 disclose the “heavyalkylate” content influences neutral sulfonates and overbasedsulfonates. In U.S. Pat. No. 5,112,506, the effect of molecular weightdistribution or “heavy alkylate” is shown to influence the performanceof both Neutral and HOB sulfonates and the di-alkylate content is shownto influence the rust performance of the corresponding sulfonate in U.S.Pat. No. 3,764,533. In U.S. Pat. No. 4,259,193, a mono-alkylatesulfonate is preferred. U.S. Pat. Nos. 3,288,716; 3,764,533; 4,259,193;and 5,112,506 are hereby incorporated by reference for all purposes.

U.S. Pat. No. 3,777,006 discloses the use of nucleating centers for thecrystallization of crystalline aluminosilicate zeolites having a size inexcess of 200 microns and characterized by high strength and excellentadsorptive properties.

U.S. Pat. No. 4,185,040 discloses the preparation of highly stable andactive catalysts for the alkylation of aromatic hydrocarbons with C₂–C₄olefins. The catalysts are acidic crystalline aluminosilicate zeoliteswhich exhibit much improved deactivation rates.

U.S. Pat. No. 4,395,372 discloses an alkylation process for alkylatingbenzene comprising contacting benzene and lower olefins with a rareearth exchanged X or Y zeolite catalyst in the presence of sulfurdioxide.

U.S. Pat. No. 4,570,027 discloses the use of a low crystallinity,partially collapsed zeolite catalyst for producing alkylaromatichydrocarbons. The alkylation reaction also involves conditioning thecatalyst bed with hydrogen prior to conducting the alkylation reaction.

U.S. Pat. Nos. 4,762,813; 4,767,734; 4,879,019 and 5,111,792 disclosethe preparation of a hydrocarbon conversion catalyst using a low silicato alumina ratio zeolite Y bound into an extrudate and steamed to modifythe catalyst.

U.S. Pat. No. 4,764,295 discloses a process for making non-foamingdetergent-dispersant lubricating oil additives. The process furtherinvolves carbonation for making the products more basic.

U.S. Pat. No. 4,876,408 discloses an alkylation process using anammonium-exchanged and steam stabilized zeolite Y catalyst having anincreased selectivity for mono-alkylation. The process involves thepresence of at least one organic compound under conditions such thatsufficient amount of carbonaceous material evenly deposits on thealkylation catalyst to substantially suppress its alkylation activity.

U.S. Pat. No. 4,891,448 discloses a process for alkylation of polycyclicaromatic compounds in the presence of an acidic mordenite zeolitecatalyst having a silica to alumina molar ratio of at least 15:1 toproduce a mixture of substituted polycyclic aromatic compounds enrichedin the para alkylated isomers.

U.S. Pat. No. 4,916,096 discloses use of a zeolite Y catalyst forhydroprocessing. The zeolite Y catalyst comprises a modified crystallinealuminosilicate zeolite Y, a binder and at least one hydrogenationcomponent of a Group VI or a Group VIII metal.

U.S. Pat. No. 5,004,841 discloses a process for alkylation of polycyclicaromatic compounds in the presence of an acidic mordenite zeolitecatalyst having a silica to alumina molar ratio of at least 15:1 toproduce substituted polycyclic aromatic compounds enriched in the linearalkylated isomers.

U.S. Pat. No. 5,026,941 discloses the use of a zeolite Y catalyst havinga silica to alumina ratio of 15 to 110 for the alkylation of naphthaleneor mono-isopropyinaphthalene.

U.S. Pat. No. 5,118,896 discloses an aromatic alkylation processcomprising the steps of contacting a hydrocarbon feed with an alkylatingagent under liquid phase alkylation conditions in the presence of asilica-containing large macropore, small particle size zeolite catalyst,the catalyst having a pore volume of about 0.25 to 0.50 cc/g in poreshaving a radius of 450 angstroms and a catalyst particle diameter of notmore than 1/32 of an inch.

U.S. Pat. No. 5,175,135 discloses the use of an acidic mordenite zeolitecatalyst for alkylation of aromatic compounds with an alkylating agenthaving from one carbon atom to eight carbon atoms to produce substitutedaromatic compounds enriched in the linear alkylated isomers. The acidicmordenite catalyst is characterized by its silica to alumina molarratio, its porosity and a Symmetry Index.

U.S. Pat. No. 5,191,135 discloses the process for making long-chainalkyl-substituted aromatic compounds from naphthalenes, the processcomprising a zeolite alkylation catalyst in the presence of 0.5 to 3.0weight percent water. The presence of water increases the selectivityfor making mono-alkylated products.

U.S. Pat. Nos. 5,240,889 and 5,324,877 disclose processes for thepreparation of a catalyst composition having alkylation and/ortransalkylation activity and wherein the catalyst composition containsgreater than 3.5 weight percent water based on the total weight of thecatalyst composition and the aromatic alkylation process using saidcatalyst composition and olefins containing 2 carbon atoms to 25 carbonatoms.

U.S. Pat. No. 5,198,595 discloses a process for alkylation of benzene orsubstituted benzene in the presence of an acidic mordenite zeolitecatalyst having a silica to alumina ratio of at least 160:1 and aSymmetry Index above about 1.0. A process for the preparation of thecatalyst is also disclosed.

U.S. Pat. No. 5,243,116 discloses the production of alkylated benzenesby alkylation and/or transalkylation in the presence of an acidicmordenite zeolite catalyst having a silica to alumina molar ration of atleast 30:1 and a specific crystalline structure determined by X-raydiffraction.

U.S. Pat. No. 5,453,553 discloses a process for the production of linearalkyl benzenes which process comprises co-feeding a mixture of benzene,linear olefins and molecular hydrogen in the presence of a zeolitecatalyst containing a transition metal under alkylation condition suchthat the catalyst is not deactivated.

U.S. Pat. No. 5,506,182 discloses the preparation of a catalystcomposition comprising 10 to 90 percent of a modified zeolite Y catalystformed from a modified zeolite Y and 10 to 90 percent binder usingslurries of the modified zeolite Y and the binder to form the catalystcomposition having a clear absorption peak in an IR spectrum of awavelength of 3602 per centimeter. The patent also discloses thesubstitution of iron for the alumina in the zeolite Y structure.

U.S. Pat. No. 5,922,922 discloses a process for isomerizing a normalalpha olefin in the presence of an acidic catalyst having aone-dimensional pore system, and then using the isomerized olefin toalkylate aromatic hydrocarbons in the presence of a second acidiccatalyst, which can be zeolite Y having a silica to alumina ratio of atleast 40 to 1.

U.S. Pat. No. 5,939,594 discloses the preparation of a superalkalinizedalkylaryl sulfonate of alkaline earth metal. The alkyl group of thealkylaryl sulfonate contains between 14 to 40 carbon atoms and the arylsulfonate radical of alkaline earth metal is fixed in a molar proportioncomprised between 0 and 13% in positions 1 or 2 of the linear alkylchain.

U.S. Pat. No. 6,031,144 discloses a process for reducing the residualolefin content of an alkylation reaction product by removing at least aportion of the non-alkylated single-ring aromatic hydrocarbon and thenreacting the remaining alkylation reaction product in the presence of anacidic catalyst such as a molecular sieve or clay.

U.S. Pat. No. 6,337,310 discloses the preparation of alkylbenzene frompreisomerized normal alpha olefins for making low overbased and highoverbased sulfonates having a TBN in the range of 3 to 500. The processuses HF as catalyst or a solid acidic alkylation catalyst, such as azeolite having an average pore size of at least 6 angstroms.

U.S. Pat. No. 6,525,234 discloses a process for alkylating aromaticusing a porous crystalline material, e.g., MCM-22 and in situregenerating the catalyst by use of a polar compound having a dipolemoment of at least 0.05 Debyes.

It is known that most solid acid catalysts produce high 2-arylattachment when alkylating with alpha-olefins. See S. Sivasanker, A.Thangaraj, “Distribution of Isomers in the Alkylation of Benzene withLong-Chain Olefins over Solid Acid Catalysts,” Journal of Catalysis,138, 386–390 (1992). This is especially true for mordenite zeolite.

Two general treatises on zeolite are: Handbook of Molecular Sieves byRosemarie Szostak (Van Nostrand Reinhold, New York 1992) and MolecularSieves: Principles of Synthesis and Identification, 2^(nd) Edition, byRosemarie Szostak (Chapman and Hall, London, UK 1999).

SUMMARY OF THE INVENTION

The present invention is directed to novel alkylated aromaticcompositions and processes for preparation of carbonated, overbasedalkylated aromatic sulfonates, which processes comprise the alkylationin the presence of the catalyst composites of this invention, andfurther sulfonation and carbonation, overbasing of the alkylatedaromatic sulfonic acids.

The present invention is also directed to zeolite catalyst compositionshaving a controlled macropore structure comprising zeolite Y andmordenite zeolite. The present invention is also directed to a processfor preparing the catalyst compositions. The catalysts and catalystcompositions exhibits reduced deactivation rates during the alkylationprocess, thereby increasing the life of the catalysts and the catalystcompositions.

In particular, the present invention is directed to an alkylatedaromatic composition comprising a mixture of:

-   -   (a) an alkylated aromatic hydrocarbon alkylation product wherein        the alkylation reaction is conducted in the presence of an        alkylation catalyst having a macropore structure comprising        zeolite Y, and wherein the peak macropore diameter of the        catalyst, measured by ASTM Test No. D 4284-03, is less than or        equal to about 2000 angstroms and the cumulative pore volume of        the catalyst at pore diameters less than or equal to about 500        angstroms, measured by ASTM Test No. D 4284-03, is less than or        equal to about 0.30 milliliters per gram; and    -   (b) an alkylated aromatic hydrocarbon alkylation product wherein        the alkylation reaction is conducted in the presence of an        alkylation catalyst having a macropore structure comprising        mordenite zeolite having a silica to alumina molar ratio of        about 50 to about 105 and wherein the peak macropore diameter of        the catalyst, measured by ASTM Test No. D 4284-03, is less than        or equal to about 900 angstroms and the cumulative pore volume        of the catalyst at pore diameters less than or equal to about        500 angstroms, measured by ASTM Test No. D 4284-03, is less than        or equal to about 0.30 milliliters per gram.

The weight percent of the alkylated aromatic hydrocarbon of (a) in themixture may be in the range of about 40 percent to about 99 percentbased on the total alkylated aromatic composition. Preferably the weightpercent of the alkylated aromatic hydrocarbon of (a) in the mixture isin the range of about 50 percent to about 90 percent based on the totalalkylated aromatic composition, and more preferably the weight percentof the alkylated aromatic hydrocarbon of (a) in the mixture is in therange of about 70 percent to about 80 percent based on the totalalkylated aromatic composition.

The alkyl groups of the alkylated aromatic composition may be derivedfrom alpha olefins, isomerized olefins, branched-chain olefins, ormixtures thereof. The alpha olefins or the isomerized olefins have fromabout 6 carbon atoms to about 40 carbon atoms. Preferably, the alphaolefins or the isomerized olefins have from about 20 carbon atoms toabout 40 carbon atoms. The branched-chain olefins have from about 6carbon atoms to about 70 carbon atoms. Preferably, the branched-chainolefins have from about 8 carbon atoms to about 50 carbon atoms. Morepreferably, the branched-chain olefins have from about 12 carbon atomsto about 18 carbon atoms.

The alkyl groups of the alkylated aromatic composition may bepartially-branched-chain isomerized olefins wherein the olefins havefrom about 6 carbon atoms to about 40 carbon atoms. Preferably, thepartially-branched-chain isomerized olefins have from about 20 carbonatoms to about 40 carbon atoms.

The aromatic hydrocarbon of the alkylated aromatic composition may bebenzene, toluene, xylene, cumene, or mixtures thereof. Preferably, thearomatic hydrocarbon is toluene or benzene.

The zeolite Y in step (a) and the mordenite zeolite in step (b) maycontain a binder. Preferably, the binder in the zeolite Y in step (a)and the binder in the mordenite zeolite in step (b) is alumina.

The zeolite Y in step (a) and the mordenite zeolite in step (b) may bein the form of a tablet.

Another embodiment of the present invention is directed to a process forpreparing an alkylated aromatic composition comprising:

-   -   (a) contacting at least one aromatic hydrocarbon with at least        one olefin under alkylation conditions in the presence of a        zeolite catalyst having a macropore structure comprising zeolite        Y, and wherein the peak macropore diameter of the catalyst,        measured by ASTM Test No. D 4284-03, is less than or equal to        about 2000 angstroms and the cumulative pore volume of the        catalyst at pore diameters less than or equal to about 500        angstroms, measured by ASTM Test No. D 4284-03, is less than or        equal to about 0.30 milliliters per gram to form a first        alkylated aromatic hydrocarbon product;    -   (b) contacting at least one aromatic hydrocarbon with at least        one olefin under alkylation conditions in the presence of a        zeolite catalyst having a macropore structure comprising        mordenite zeolite having a silica to alumina molar ratio of        about 50 to about 105, and wherein the peak macropore diameter        of the catalyst, measured by ASTM Test No. D 4284-03, is less        than or equal to about 900 angstroms and the cumulative pore        volume of the catalyst at pore diameters less than or equal to        about 500 angstroms, measured by ASTM Test No. D 4284-03, is        less than or equal to about 0.30 milliliters per gram to form a        second alkylated aromatic hydrocarbon product; and    -   (c) combining the first alkylated aromatic hydrocarbon product        and the second alkylated aromatic hydrocarbon product to form        the alkylated aromatic composition;        wherein steps (a) and (b) can be conducted in any order.

The above process may further comprise in step (b) the reactivation ofthe deactivated zeolite catalyst with a suitable solvent flush,preferably the solvent is an aromatic hydrocarbon. More preferably, thearomatic hydrocarbon is benzene.

The above process may further comprise sulfonating the alkylatedaromatic composition to form an alkylated aromatic sulfonic acid. Thealkylated aromatic sulfonic acid may be reacted with an alkaline earthmetal and carbon dioxide to produce a carbonated, overbased alkylatedaromatic sulfonate.

The first alkylated aromatic hydrocarbon product in the alkylatedaromatic composition may be in the range of about 40 percent to about 99percent based on the total alkylated aromatic composition. Preferably,the first alkylated aromatic hydrocarbon product in the alkylatedaromatic composition is in the range of about 50 percent to about 90percent based on the total alkylated aromatic composition. Morepreferably, the first alkylated aromatic hydrocarbon product in thealkylated aromatic composition is in the range of about 70 percent toabout 80 percent based on the total alkylated aromatic composition.

The olefin in step (a) and step (b) may be independently an alphaolefin, an isomerized olefin, a branched-chain olefin, or mixturesthereof. The alpha olefin or isomerized olefin may have from about 6carbon atoms to about 40 carbon atoms. Preferably, the alpha olefin orisomerized olefin has from about 20 carbon atoms to about 40 carbonatoms. The branched-chain olefin may have from about 6 carbon atoms toabout 70 carbon atoms. Preferably, the branched-chain olefin has fromabout 8 carbon atoms to about 50 carbon atoms. More preferably, thebranched-chain olefin has from about 12 carbon atoms to about 18 carbonatoms.

The olefin in step (a) or step (b) may be independently apartially-branched-chain isomerized olefin, and the olefin may have fromabout 6 carbon atoms to about 40 carbon atoms. Preferably, thepartially-branched-chain isomerized olefin has from about 20 carbonatoms to about 40 carbon atoms.

The aromatic hydrocarbon of the alkylated aromatic composition may bebenzene, toluene, xylene, cumene, or mixtures thereof. Preferably, thearomatic hydrocarbon is toluene or benzene.

The cumulative pore volume of the zeolite catalyst at pore diametersless than or equal to about 400 angstroms in step (a) and step (b) isless than or equal to about 0.30 milliliters per gram. Preferably,cumulative pore volume of the zeolite catalysts at pore diameters lessthan or equal to about 300 angstroms in steps (a) and (b) is less thanabout 0.25 milliliters per gram, more preferably at pore diameters lessthan or equal to about 300 angstroms is less than about 0.20 millilitersper gram, and most preferably at pore diameters less than or equal toabout 300 angstroms is in the range of about 0.08 milliliters per gramto about 0.16 milliliters per gram.

The cumulative pore volume of the zeolite catalysts at pore diametersless than or equal to about 400 angstroms in steps (a) and (b) is in therange of about 0.05 milliliters per gram to about 0.18 milliliters pergram. Preferably, the cumulative pore volume of the zeolite catalysts atpore diameters less than or equal to about 300 angstroms in steps (a)and (b) is in the range of about 0.08 milliliters per gram to about 0.16milliliters per gram.

The zeolite Y catalyst in step (a) has a peak macropore diameter in therange of about 700 angstroms to about 1800 angstroms. Preferably, thepeak macropore diameter of the zeolite Y catalyst in step (a) is in therange of about 750 angstroms to about 1600 angstroms. More preferably,the peak macropore diameter of the zeolite Y catalyst in step (a) is inthe range of about 900 angstroms to about 1400 angstroms.

In step (b), the peak macropore diameter of the mordenite zeolitecatalyst is in the range of about 400 angstroms to about 800 angstroms.Preferably in step (b), the peak macropore diameter of the mordenitezeolite catalyst is in the range of about 400 angstroms to about 700angstroms. More preferably in step (b), the peak macropore diameter ofthe mordenite zeolite catalyst is in the range of about 450 angstroms toabout 600 angstroms.

In steps (a) in the above process, the zeolite Y catalyst has a silicato alumina ratio of about 5:1 to about 100:1. Preferably in step (a),the zeolite Y catalyst has a silica to alumina ratio of about 30:1 toabout 90:1. More preferably in step (a), the zeolite Y catalyst has asilica to alumina ratio of about 60:1 to about 80:1.

In step (b) in the above process, preferably the mordenite zeolitecatalyst has a silica to alumina ratio of about 60:1 to about 80:1.

The zeolite Y in step (a) and the mordenite zeolite in step (b) maycontain a binder. Preferably, the binder in the zeolite Y in step (a)and the binder in the mordenite zeolite in step (b) is alumina.

The zeolite Y in step (a) and the mordenite zeolite in step (b) may bein the form of a tablet.

A further embodiment of the present invention is directed to a processfor preparing an alkylated aromatic composition comprising contacting atleast one aromatic hydrocarbon with at least one olefin in the presenceof a zeolite catalyst having a macropore structure comprising zeolite Yand mordenite zeolite having a silica to alumina ratio of about 50:1 toabout 105:1, and wherein the peak macropore diameter of the catalyst,measured by ASTM Test No. D 4284-03, is less than or equal to about 2000angstroms and the cumulative pore volume of the catalyst at porediameters less than or equal to about 500 angstroms, measured by ASTMTest No. D 4284-03, is less than or equal to about 0.30 milliliters pergram.

The cumulative pore volume of the zeolite catalyst at pore diametersless than or equal to about 400 angstroms is less than or equal to about0.30 milliliters per gram. Preferably, the cumulative pore volumezeolite catalyst at pore diameters less than or equal to about 300angstroms is less than or equal to about 0.25 milliliters per gram. Morepreferably, the cumulative pore volume zeolite catalyst at porediameters less than or equal to about 300 angstroms is less than orequal to about 0.20 milliliters per gram.

The cumulative pore volume of the zeolite catalyst at pore diametersless than or equal to about 400 angstroms may be in the range of about0.05 milliliters per gram to about 0.18 milliliters per gram.Preferably, the cumulative pore volume of the zeolite catalyst at porediameters less than or equal to about 300 angstroms is in the range ofabout 0.08 milliliters per gram to about 0.16 milliliters per gram.

The peak macropore diameter of the zeolite catalyst is in the range ofabout 400 angstroms to about 1500 angstroms. Preferably, the peakmacropore diameter of the zeolite catalyst is in the range of about 500angstroms to about 1300 angstroms. More preferably the peak macroporediameter of the zeolite catalyst is in the range of about 600 angstromsto about 1100 angstroms, and most preferably the peak macropore diameterof the zeolite catalyst is in the range of about 750 angstroms to about900 angstroms.

The zeolite Y has a silica to alumina molar ratio of about 5:1 to about100:1 and the mordenite zeolite has a silica to alumina molar ratio ofabout 50:1 to about 105:1. Preferably the zeolite Y has a silica toalumina molar ratio of about 30:1 to about 90:1, and more preferably thezeolite Y and the mordenite zeolite independently has a silica toalumina molar ratio of about 60:1 to about 80:1.

The zeolite catalyst may contain a binder. Preferably, the binder isalumina.

The zeolite catalyst may be in the form of a tablet.

Yet another embodiment of the present invention is directed to a zeolitecatalyst composition having a macropore structure comprising:

-   -   (a) zeolite Y; and    -   (b) mordenite zeolite having a silica to alumina molar ratio in        the range of about 50:1 to about 105:1;        wherein the peak macropore diameter of the catalyst composition,        measured by ASTM Test No. D 4284-03, is less than about 2000        angstroms and the cumulative pore volume of the catalyst at pore        diameters less than or equal to about 500 angstroms, measured by        ASTM Test No. D 4284-03, is less than or equal to about 0.30        milliliters per gram.

The cumulative pore volume of the zeolite catalyst composition at porediameters less than or equal to about 400 angstroms is less than orequal to about 0.30 milliliters per gram. Preferably, the cumulativepore volume zeolite catalyst composition at pore diameters less than orequal to about 300 angstroms is less than or equal to about 0.25milliliters per gram. More preferably, the cumulative pore volumezeolite catalyst composition at pore diameters less than or equal toabout 300 angstroms is less than or equal to about 0.20 milliliters pergram.

The cumulative pore volume of the zeolite catalyst composition at porediameters less than or equal to about 400 angstroms may be in the rangeof about 0.05 milliliters per gram to about 0.18 milliliters per gram.Preferably, the cumulative pore volume of the zeolite catalystcomposition at pore diameters less than or equal to about 300 angstromsis in the range of about 0.08 milliliters per gram to about 0.16milliliters per gram.

The peak macropore diameter of the zeolite catalyst composition is inthe range of about 400 angstroms to about 1500 angstroms. Preferably,the peak macropore diameter of the zeolite catalyst composition is inthe range of about 500 angstroms to about 1300 angstroms. Morepreferably the peak macropore diameter of the zeolite catalystcomposition is in the range of about 600 angstroms to about 1100angstroms, and most preferably the peak macropore diameter of thezeolite catalyst composition is in the range of about 750 angstroms toabout 900 angstroms.

The zeolite Y in step (a) having a silica to alumina ratio of about 5:1to about 100:1, preferably the zeolite Y has a silica to alumina molarratio of about 30:1 to about 90:1, and more preferably the zeolite Y hasa silica to alumina molar ratio of about 60:1 to about 80:1.

The mordenite zeolite in step (b) preferably has a silica to aluminamolar ratio of about 60:1 to about 80:1.

The zeolite catalyst composition may contain a binder. Preferably, thebinder is alumina.

The zeolite catalyst composition may be in the form of a tablet.

DETAILED DESCRIPTION OF THE INVENTION Definitions

The term “alkylate” means an alkylated aromatic hydrocarbon.

The term “2-aryl content” is defined as the percentage of total alkylate(the alkylate species in which the alkyl chain derived from the olefinemployed in the present alkylation process is attached to the aromaticring) that is comprised of those chemical species in which theattachment of the alkyl chain to the aromatic ring is at the 2-positionalong the alkyl chain.

The term “binder” means any suitable inorganic material which can serveas matrix or porous matrix to bind the zeolite particles into a moreuseful shape.

The term “branched-chain olefins” means olefins derived from thepolymerization of olefin monomers higher than ethylene and containing asubstantial number of branches wherein the branches are alkyl groupshaving from about one carbon atom to about 30 carbon atoms. Mixtures ofethylene and higher olefins are also contemplated.

The term “calcining” as used herein means heating the catalyst to about400° C. to about 1000° C. in a substantially dry environment.

The term “carbonated, overbased” is used to describe those alkalineearth metal alkyl aromatic sulfonates in which the ratio of the numberof equivalents of the alkaline earth metal moiety to the number ofequivalents of the aromatic sulfonic acid moiety is greater than one,and is usually greater than 10 and may be as high as 20 or greater.

The term “cumulative pore volume” obtained by Mercury IntrusionPorosimetry as used herein refers to that part of the total volume inmilliliters per gram derived from the graphical, cumulative pore volumedistribution, measured by Section 14.1.6 of ASTM D 4284-03, or thecorresponding tabular presentation of the same data between definedupper and lower pore diameters. When no lower diameter limit is defined,the lower limit is the lowest detection limit or lowest radius measuredby Section 14.1.6 of ASTM D 4284-03.

The terms “dry basis”, “anhydrous basis”, and “volatiles-free basis”shall refer to the dry weight of catalyst composite or raw materialsexpressed on a metal oxides basis such as Na₂O.Al₂O₃.xSiO₂.

The term “flush” as used herein means contacting the deactivatedmordenite catalysts and mordenite catalyst composites of this inventionin the reactor with a suitable solvent, such as an aromatic hydrocarbonfor reactivation of the mordenite catalysts and mordenite catalystcomposites.

The term “loss-on-ignition (LOI)” as used herein means the percentweight loss of the zeolite composite and raw material samples whichvolatilize or evaporate when heated to 538° C. for 1 hour. When thetemperature is greater than or equal about 538° C., the“loss-on-ignition” approximates the percent volatiles.

The terms “macropore”, “mesopore”, and “micropore” as used herein followthe definitions set forth by the International Union of Pure and AppliedChemistry (IUPAC), Division of Physical Chemistry, in Manual of Symbolsand Terminology for Physicochemical Quantities and Units, Appendix IIDefinitions, Terminology and Symbols in Colloid and Surface ChemistryPart I, Adopted by the IUPAC Council at Washington, D.C., USA, on 23Jul., 1971. Pores with widths or diameters exceeding ˜50 nanometers (500angstroms) are called “macropores”. Pores with widths or diameters notexceeding ˜2.0 nanometers (20 angstroms) are called “micropores”. Poresof intermediate size (2.0 nanometers<width or diameter≦50 nm) are called“mesopores”.

The term “Mercury Intrusion Porosimetry” refers to the ASTM Test No. D4284-03 used to determine pore volume distribution of catalysts byMercury Intrusion Porosimetry. Mercury pore distribution was measuredusing a Quantachrome Scanning Mercury Porosimeter Model SP-100. Thesoftware version used by the instrument is V2.11 (dated Oct. 27, 1993).Surface tension used in the calculation is 473 dynes per centimeter andthe contact angle is 140 degrees.

The terms “normal alpha olefin” and “linear alpha olefin” mean thosestraight-chain olefins without a significant degree of alkyl branchingin which the carbon to carbon double bond resides primarily at the endor “alpha” position of the carbon chain, i.e., between C₁ and C₂. Normalalpha olefins are derived from polymerization of ethylene.

The term “normal alpha olefin isomerization” means the conversion ofnormal alpha olefins into isomerized olefins having a lower alpha olefincontent (the double bond is between C₁ and C₂), higher internal olefincontent (the double bond is in positions other than between C₁ and C₂),and optionally a higher degree of branching.

The term “partially-branched chain olefin” is defined as the olefinproduct of isomerization of normal alpha olefins wherein the degree ofbranching is higher than in the starting normal alpha olefins.

The term “peak macropore diameter” as used herein means the peakdiameter (i.e., the diameter within the macropore region at which thedifferential plot of pore size distribution, as defined by Section 14.2,reaches a maximum) in the macropore range determined by ASTM Test No.4284-03 for the macropore peak in the catalysts of the presentinvention.

The term “peptizing” means the dispersion of large aggregates of binderparticles, including hydrated aluminas, into much smaller primaryparticles by the addition of acid.

The term “percent volatiles” as used herein means the difference betweenthe actual weight of the catalyst composite or the raw materials and theweight of the material on a dry, anhydrous, or volatiles-free basis,expressed as a percentage of the actual sample weight.

The term “SAR” or “silica to alumina ratio” refers to the molar ratio ofsilicon oxide to aluminum oxide; mol SiO₂:mol AlO₃.

The term “sufficient water to shape the catalyst material” meansquantity of water required to make an acid peptized mixture of zeoliteand alumina powders into an extrudable mass.

The term “tabletting” as used herein refers to the process of forming acatalyst aggregate from zeolite powder or a mixture of zeolite andbinder powders by compressing the powder in a die.

The term “total pore volume” obtained by Mercury Intrusion Porosimetryas used herein refers to the total pore volume in milliliters per gramderived from the graphical, cumulative pore volume distribution (Section14.1.6 of ASTM D 4284-03) or the corresponding tabular presentation ofthe same data.

As used herein, all percentages are weight percent, unless otherwisespecified.

As noted above, the present invention is directed to novel alkylatedaromatic compositions and their sulfonated and carbonated products. Thealkylation of the aromatic hydrocarbons is carried out in the presenceof the zeolite catalyst compositions of the present invention having acontrolled macropore structure comprising zeolite Y and mordenitezeolite. The catalysts of the present invention were characterized bypore volume distribution obtained by Mercury Intrusion Porosimetry, ASTMTest No. D 4284-03. Mercury Intrusion Porosimetry provides a graph ofcumulative pore volume (pv) versus pore diameter (pd). Mercury IntrusionPorosimetry also is used to determine the macropore peak diameter fromthe derivative, delta pv (Δpv) divided by delta pd (Δpd). The graphs areused to characterize the catalysts of the present invention.

The zeolite catalyst compositions were prepared using zeolite Y andmordenite zeolite. Zeolite Y and mordenite zeolite may also be combinedto prepare zeolite catalyst compositions of the present invention. Whenthe zeolite catalyst compositions contain both zeolite Y and mordenitezeolite, the zeolite catalyst composite may be prepared by mixingzeolite Y and mordenite zeolite powders before the binding and shapingsteps. The zeolite Y CBV 760® and CBV 600® available from ZeolystInternational having a nominal silica to alumina ratio of 60 and 6.7,respectively, may be used for preparing the zeolite catalystcompositions of this invention. However, zeolite Y having a silica toalumina ratio between 5 and 110 may be used for the preparation of thezeolite catalysts compositions of the present invention. The mordenitezeolite 90A® having a nominal silica to alumina ratio of 90, alsoavailable from Zeolyst International, may be used for preparing thezeolite catalyst compositions of this invention. Mordenite zeolitehaving a silica to alumina ratio of 50 to 105 may be used in thepreparation of the zeolite catalyst compositions of this invention.

The catalysts of the present invention may be shaped or formed intotablets, extrudates or any other shape using procedures well known inthe prior art. The preparation of extrudates requires the presence of abinder, such as alumina. The tabletted catalysts do not require thepresence of a binder, but a binder may be present in a tabletted zeolitecatalyst. The crystalline zeolite powder may be compressed to form atablet. The tabletted catalysts of the present invention provideexceptionally low deactivation rates in alkylation reactions.

The alkylation of aromatic hydrocarbons with one or more olefins may becarried out in a fixed bed reactor in the presence of the zeolitecatalysts compositions of the present invention comprising only zeoliteY, only mordenite zeolite, or both zeolite Y and mordenite zeolite. Thealkylation process is conducted without the addition of water and usingdried aromatic hydrocarbon and olefin feed. It is believed that thepresence of water during the alkylation increases the deactivation rateof the catalysts of this invention. When the alkylation using zeolite Yand mordenite zeolite is carried out in separate fixed bed reactors, thealkylated aromatic hydrocarbons may be combined to obtain the desiredamount of alpha olefins versus branched-chain olefins. Alkylationreactions using normal alpha olefins and zeolite catalysts compositionscomprising only mordenite zeolite give predominantly alkylated aromatichydrocarbons wherein the attachment of the of the alkyl chain to thearomatic ring is at the 2-position along the alkyl chain. On the otherhand, alkylation reactions using zeolite catalysts compositionscomprising only zeolite Y and normal alpha olefins give predominantlyattachments at other than the 2-position along the alkyl chain.

The alkylation reaction may be carried out by any conventionally knownprocess. The aromatic hydrocarbon is reacted with one or more olefins inthe presence of a catalyst of the present invention under alkylationreaction conditions. The above alkylation process is conducted withoutthe addition of water and using dried aromatic hydrocarbon and olefinfeed. It is believed that the presence of water during the alkylationprocess increases the deactivation rate of the catalysts of thisinvention.

The aromatic hydrocarbon may be single-ring or double-ring, preferablythe aromatic hydrocarbon is a single-ring aromatic hydrocarbon. Thearomatic hydrocarbon may be an alkylated aromatic hydrocarbon, such as amono-alkylated aromatic hydrocarbon, wherein the alkyl group has fromabout 4 carbon atoms to about 80 carbon atoms. When the aromatichydrocarbon used is a mono-alkylated aromatic, the product of thealkylation reaction is a di-alkylated aromatic hydrocarbon.

The olefins useful for alkylation of the aromatic hydrocarbons may belinear-chain olefins or branched-chain olefins having from about 4carbon atoms to about 80 carbon atoms. In addition, normal alpha olefinsmay be isomerized to obtain partially-branched-chain olefins for use inalkylation process of the present invention. These resultingpartially-branched-chain olefins may be alpha-olefins, beta-olefins,internal-olefins, tri-substituted olefins, and vinylidene olefins.

Alkylated aromatic hydrocarbon sulfonic acids of the alkylated aromatichydrocarbons of the present invention may be prepared by any knownsulfonation reaction. The alkylated aromatic sulfonic acids may befurther reacted with an alkaline earth metal and carbon dioxide toobtain carbonated, overbased alkylated aromatic sulfonates useful asdetergents in lubricating oils. Carbonation may be carried out by anyconventionally known process. The degree of overbasing may be controlledby changing the reaction conditions and the amount of the alkaline earthmetal and carbon dioxide used in the carbonation process.

The novel alkylation compositions of the present invention may beobtained by conducting the alkylation reactions as described above inthe presence of the zeolite catalyst compositions of the presentinvention prepared as described in Examples 1–4 below.

Procedure for Isomerization of Normal Alpha Olefins

The isomerization process may be carried out in batch or continuousmode. The process temperatures can range from 50° C. to 250° C. In thebatch mode, a typical method is to use a stirred autoclave or glassflask, which may be heated to the desired reaction temperature. Acontinuous process is most efficiently carried out in a fixed bedprocess. Space rates in a fixed bed process can range from 0.1 to 10 ormore weight hourly space velocity.

In a fixed bed process, the isomerization catalyst is charged to thereactor and activated or dried at a temperature of at least 150° C.under vacuum or flowing inert, dry gas. After activation, thetemperature of the isomerization catalyst is adjusted to the desiredreaction temperature and a flow of the olefin is introduced into thereactor. The reactor effluent containing the partially-branched,isomerized olefins is collected. The resulting partially-branched,isomerized olefins contain a different olefin distribution (alphaolefin, beta olefin, internal olefin, tri-substituted olefin, andvinylidene olefin) and branching content than the unisomerized olefin.

Procedure for Alkylation of Aromatic Hydrocarbons

Alkylation of aromatic hydrocarbons with normal alpha olefins,partially-branched-chain isomerized olefins, and branched-chain olefinsmay be carried out by any method known by a person skilled in the art.

The alkylation reaction is typically carried out with an aromatichydrocarbon and an olefin in molar ratios from 1:15 to 25:1. Processtemperatures can range from about 100° C. to about 250° C. The processis carried out without the addition of water. As the olefins have a highboiling point, the process is preferably carried out in the liquidphase. The alkylation process may be carried out in batch or continuousmode. In the batch mode, a typical method is to use a stirred autoclaveor glass flask, which may be heated to the desired reaction temperature.A continuous process is most efficiently carried out in a fixed bedprocess. Space rates in a fixed bed process can range from 0.01 to 10 ormore weight hourly space velocity.

In a fixed bed process, the alkylation catalyst is charged to thereactor and activated or dried at a temperature of at least 150° C.under vacuum or flowing inert, dry gas. After activation, the alkylationcatalyst is cooled to ambient temperature and a flow of the aromatichydrocarbon compound is introduced, optionally toluene. Pressure isincreased by means of a back pressure valve so that the pressure isabove the bubble point pressure of the aromatic hydrocarbon feedcomposition at the desired reaction temperature. After pressurizing thesystem to the desired pressure, the temperature is increased to thedesired reaction temperature. A flow of the olefin is then mixed withthe aromatic hydrocarbon and allowed to flow over the catalyst. Thereactor effluent comprising alkylated aromatic hydrocarbon, unreactedolefin and excess aromatic hydrocarbon compound are collected. Theexcess aromatic hydrocarbon compound is then removed by distillation,stripping, evaporation under vacuum, or any other means known to thoseskilled in the art.

Procedure for Sulfonation of Alkylated Aromatic Hydrocarbons

Sulfonation of alkylated hydrocarbons may be carried out by any methodknown by a person skilled in the art.

The sulfonation reaction is typically carried out in a falling filmtubular reactor maintained at about 65° C. The alkylated aromatichydrocarbon is placed in the tube and sulfur trioxide diluted withnitrogen is added to the alkylated aromatic hydrocarbon. The molar ratioof alkylated aromatic hydrocarbon to sulfur trioxide is maintained atabout 1.05:1. The resulting alkylated aromatic sulfonic acid may bediluted with about 10% 100 Neutral oil followed by thermal treatmentwith nitrogen bubbling at a rate of about 10 liters per kilogram ofproduct and stirring while maintaining the temperature at about 85° Cuntil the desired residual sulfuric acid content is obtained (maximum ofabout 0.5%).

Procedure for Carbonation, Overbasing of Alkylated Aromatic SulfonicAcids

Carbonation, overbasing of alkylaromatic sulfonic acids may be carriedout by any method known by a person skilled in the art to producealkylaromatic sulfonates.

Generally, the carbonation, overbasing reaction is carried out in areactor in the presence of the alkylated aromatic sulfonic acid, diluentoil, an aromatic solvent, and an alcohol. The reaction mixture isagitated and alkaline earth metal and carbon dioxide are added to thereaction while maintaining the temperature between about 20° C. and 80°C.

The degree of carbonation, overbasing may be controlled by the quantityof the alkaline earth metal and carbon dioxide added to the reactionmixture, the reactants and the reaction conditions used during thecarbonation process.

Reactivation of Deactivated Mordenite Zeolite Catalysts and Composites

Once the mordenite zeolite catalysts and catalyst composites arecompletely deactivated, the alkylation reaction stops because of thepolymerization of the olefin into large molecular species that cannotdiffuse out of the crystal micropores containing the active sites in thezeolitic material. However, reactor bed need not be changed to removethe deactivated mordenite zeolite catalysts and catalyst composites. Thedeactivated mordenite zeolite catalysts and catalyst composites arereactivated at the end of an alkylation run by stopping the olefin feedstream to the reactor and permitting the aromatic hydrocarbon stream tocontinue to be flushed through the reactor for a sufficient time,typically from about 12 hours to about 24 hours.

EXAMPLES Example 1 Preparation of Zeolite Catalyst Composition 1

Zeolite Catalyst Composition 1 is prepared by mixing zeolite Y powderand mordenite zeolite powder available from Zeolyst International or anyother commercial source. The zeolite Y and mordenite zeolite powders aremixed in any proportion based on the desired alkylated aromatic product.

As an example, zeolite Y catalyst powder is mixed with mordenite zeolitecatalyst powder to obtain a final ratio of 85:15 in the final ZeoliteCatalyst Composition.

Zeolite Catalyst Composition 1 is prepared by the following method:

Loss-on-ignition (LOI) is determined for samples of commerciallyavailable zeolite Y (CBV 760® and CBV 600®) and mordenite zeolite (CBV90A®) available from Zeolyst International by heating the samples to538° C. for 1 hour. The LOI obtained provides the percent volatiles inthe zeolite Y and mordenite zeolite batches being used. The LOI of acommercial sample of Versal® hydrated aluminum oxide available fromSasol is also obtained by heating the samples to 538° C. for 1 hour.Next, based on the results obtained from the LOI of the zeolite Y,mordenite zeolite and the alumina powders the amount of alumina powderis weighed out to obtain 80% (volatile-free basis) zeolite content ofthe composite consists of 85% zeolite Y and 15% mordenite zeolite on avolatile-free basis.

The three dry powders are added to a Baker Perkins mixer and dry mixedfor 4 minutes. The amount of concentrated (70.7%) nitric acid to give0.7 weight % (based on 100% nitric acid) of the dry weight of thezeolite and the alumina powders is calculated. This amount of 70.7%nitric acid was weighed out and dissolved in deionized water.

The total amount of water and 70.7% nitric acid needed to obtain a finalconcentration of approximately 50% total volatiles is calculated asfollows. Volatiles in the Y zeolite, mordenite zeolite and aluminapowders is calculated. Nitric acid solution is considered to be 100%volatiles. Thus, the amount of deionized water that must be added is thedifference between the final concentration of volatiles of 50% minus thetotal volatiles in the three powders.

Deionized water is added over a period of 5 minutes to the powders inthe mixer using a peristaltic pump. The mixer is then stopped so thatthe walls of the mixer can be scraped down. Mixing is then resumed andthe solution of nitric acid in water is added over 5 minutes using theperistaltic pump. At the end of acid addition, mixing is continued for atotal time of 40 minutes, with occasional holds to allow for scrapingthe sides of the mixer. At the end of the mixing period, the percentvolatiles are measured. Additional amounts of deionized water is addeduntil the mixture appears extrudable and the percent volatiles are againmeasured.

The wet mixture is extruded through 1.27 millimeters, asymmetricquadrilobe die inserts, in a Bonnot extruder. The wet long cylindricalstrands are dried at 121° C. for 8 hours. The long cylindrical strandsare then broken to give extrudates with length to diameter ratio of 2:6.The extrudates are sieved and the portion larger than 1.0 millimeter isretained.

The extrudates are then calcined in a muffle furnace using the followingtemperature program:

The extrudates are heated to 593° C. over two hours, then held at 593°C. for ½ hour and next cooled to 204° C. A total weight of theextrudates is obtained.

Mercury Intrusion Porosimetry is used to characterize the extrudates. Apeak macropore diameter in angstroms and a cumulative pore volume atdiameters less than 300 angstroms is obtained from the Mercury IntrusionPorosimetry data.

The Zeolite Catalyst Composition is charged to a pilot plant reactorused for the alkylation of aromatic hydrocarbons. The reaction effluentof this reactor has greater than or equal to 99% conversion of theolefin feed stream. When benzene is used as the aromatic hydrocarbon andthe alkylation reaction is conducted using the Zeolite CatalystComposition, there is a much higher attachment of the alkyl chain to thearomatic ring at the 2-position along the alkyl chain in the alkylatedbenzene than when the zeolite Y catalyst composite is used alone in thealkylation reaction.

Excess benzene is removed by distillation, stripping or any othersuitable means and the alkylated benzene is sulfonated using sulfonationprocedures well known in the art. The alkyl benzene sulfonic acid isfurther carbonated with an alkaline earth metal and carbon dioxide.

Example 2 Preparation of Zeolite Y Catalyst Composite

Zeolite Y Catalyst Composite was prepared are described above in Example1 using zeolite Y CBV 760® available from Zeolyst International.

Example 3 Preparation of Mordenite Zeolite Catalyst Composite

Mordenite Zeolite Catalyst Composite was prepared are described above inExample 1 using mordenite zeolite CBV 90A® available from ZeolystInternational.

Example 4 Preparation of Zeolite Catalyst Composition 2

Zeolite Catalyst Composition 2 is prepared by mixing Zeolite Y CatalystComposite and Mordenite Zeolite Catalyst Composite prepared in Examples2 and 3. The Zeolite Y Catalyst Composite and Mordenite Zeolite CatalystComposite are mixed in any proportion based on the desired alkylatedaromatic product. As an example, Zeolite Y Catalyst Composite is mixedwith Mordenite Zeolite Catalyst Composite to obtain a final ratio of85:15 in the Zeolite Catalyst Composition 2.

The resulting Zeolite Catalyst Composition 2 is charged to a pilot plantreactor for the alkylation of aromatic hydrocarbons as described belowin Example 5.

Example 5 Preparation of Alkylbenzene Compositions Using Zeolite YCatalyst Composite

Typically, alkylation of aromatic hydrocarbons with normal alphaolefins, partially-branched-chain isomerized olefins and branched-chainolefins was carried out as described below:

A fixed bed reactor constructed from 15.54 millimeters Schedule 160stainless steel pipe was used for this alkylation test. Pressure in thereactor was maintained by an appropriate back pressure valve. Thereactor and heaters were constructed so that adiabatic temperaturecontrol could be maintained during the course of alkylation runs. A 192gram bed of 850 micrometer to 2 millimeters Alundum particles was packedin the bottom of the reactor to provide a pre-heat zone. Next, 100 gramsof a zeolite Y catalyst composite similar to the zeolite Y catalystcomposite prepared in Example 2 above was charged to the fixed bedreactor. The reactor was gently vibrated during loading to give amaximum packed bulk density of catalyst in the reactor. Finally, voidspaces in the catalyst bed were filled with 351 grams 150 micrometersAlundum particles as interstitial packing. The reactor was then closed,sealed, and pressure tested under nitrogen. Next, the alkylationcatalyst was dehydrated during 15 hours at 200° C. under a 20 liters perhour flow of nitrogen measured at ambient temperature and pressure andthen cooled to 100° C. under nitrogen. Benzene was then introduced intothe catalytic bed in an up-flow manner at a flow rate of 195 grams perhour. Temperature (under adiabatic temperature control) was increased toa start-of-run temperature of 182° C. (measured just before the catalystbed) and the pressure was increased to 14.6 atmospheres. Whentemperature and pressure had lined out at desired start-of-runconditions of 182° C. and 14.6 atmospheres, a feed mixture, consistingof benzene and C₂₀₋₂₄ NAO at a molar ratio of 10:1 and dried overactivated alumina, was introduced in an up-flow manner. As the feedreached the catalyst in the reactor, reaction began to occur andinternal catalyst bed temperatures increased above the inlettemperature. After about 8 hours on-stream, the reactor exotherm was 20°C. At 26 hours on-stream, the olefin conversion in the product was99.1%. The run was stopped after 408 hours on-stream, although the runcould have continued. At this time, the olefin conversion was 99.45%.

Alkylated aromatic hydrocarbon products containing excess benzene werecollected during the course of the run. After distillation to removeexcess aromatic hydrocarbon, analysis showed that greater than 99%conversion of olefin was achieved during the course of the run.

A fixed bed reactor was constructed from 15.54 millimeters Schedule 160stainless steel pipe. Pressure in the reactor was maintained by anappropriate back pressure valve. The reactor and heaters wereconstructed so that adiabatic temperature control could be maintainedduring the course of alkylation runs. A small amount of 850 micrometerto 2 millimeters acid-washed Alundum was packed in the bottom of thereactor to provide a pre-heat zone. Next, 100 grams of whole alkylationextrudate catalyst was charged to the fixed bed reactor. Finally, voidspaces in the catalyst bed were filled with 150 micrometers acid-washedAlundum interstitial packing. The zeolite Y or the mordenite zeolitealkylation catalyst was then dehydrated for at least 8 hours at 200° C.under a flow of nitrogen gas and then cooled to ambient temperatureunder nitrogen gas. Benzene was then introduced into the catalytic bedin an up-flow manner. Temperature (isothermal temperature control) andpressure were increased at start of run conditions. Normal operatingpressure was 11.91 atmospheres. The initial temperature of approximately150° C. was chosen so that the temperature in the catalytic bedincreased under adiabatic temperature control to about 160° C. to about175° C. When temperature and pressure had lined out at desiredstart-of-run conditions, the reactor system was switched to adiabatictemperature control. A dried feed mixture, consisting of olefin andbenzene, was introduced in an up-flow manner. The benzene to olefinmolar ratio was 10:1. As the reaction began to occur, temperatureincreased in the catalyst bed above the inlet temperature.

Alkylated benzene product containing excess benzene was collected duringthe course of the run. After distillation to remove excess benzene,analysis showed that greater than 99% conversion of olefin was achievedduring the course of the run.

Example 6 Preparation of Alkylbenzene Compositions

Typically, alkylation of aromatic hydrocarbons with normal alphaolefins, partially-branched-chain isomerized olefins and branched-chainolefins was carried out as described below:

A fixed bed reactor was constructed from 15.54 millimeters Schedule 160stainless steel pipe. Pressure in the reactor was maintained by anappropriate back pressure valve. The reactor and heaters wereconstructed so that adiabatic temperature control could be maintainedduring the course of alkylation runs. A bed of 170 grams of 850micrometer to 2 millimeters Alundum particles was packed in the bottomof the reactor to provide a pre-heat zone. Next, 100 grams of mordenitecatalyst composite similar to the mordenite catalyst composite preparedin Example 3 above was charged to the fixed bed reactor. Finally, voidspaces in the catalyst bed were filled with 309 grams of 150 micrometersAlundum particles interstitial packing. The reactor was gently vibratedwhile charging catalyst and alundum to ensure a high packed bulkdensity. After charging, the reactor was closed, sealed, and thepressure was tested.

The alkylation catalyst was then heated to 200° C. under a 20 liters perhour flow of nitrogen measured at ambient temperature and pressure anddehydrated for 23 hours at 200° C. The catalyst bed was then cooled to100° C. under nitrogen. Benzene was then introduced into the catalyticbed in an up-flow manner at a flow rate of 200 grams per hour.Temperature (under adiabatic temperature control) was increased to astart of run inlet temperature of 154° C. (measured just before thecatalyst bed) and the pressure was increased to 12.66 atmospheres.

When temperature and pressure had lined out at desired start-of-runconditions of 154° C. and 12.66 atmospheres, a feed mixture, consistingof benzene and C₂₀₋₂₄ NAO at a molar ratio of 15:1 and dried overactivated alumina, was introduced in an up-flow manner at 200 grams perhour. As the feed reached the catalyst in the reactor, reaction began tooccur and internal catalyst bed temperatures increased above the inlettemperature. After about 8 hours on-stream, the reactor exotherm was 20°C. In the first 57 hours on-stream, the olefin conversion decreased from100% to 98.8% (Run Period 1). At this point, the catalyst bed wasflushed with benzene at 200 grams per hour during 18 hours. Followingthe benzene flush, the benzene and olefin feed flow was resumed. Inlettemperature was increased to 162° C. at 57 run hours. Feed was continueduntil 351 run hours (Run Period 2 from 57 to 351 run hours). Olefinconversion was initially 98.9% during Run Period 2 but declined to 98.1%at 321 run hours and further to 95.3% at 351 run hours. A second benzeneflush was performed at 351 run hours during 17 hours. After the secondbenzene flush, feed flow was resumed again to start Run Period 3. Feedwas continued until 550 run hours. Olefin conversion was initially 98.5%but declined to 98.3% at 519 run hours and to 97.0% at 550 run hours. Athird benzene flush was done during a weekend. Feed flow was resumedafter the third benzene flush to begin Run Period 4. At the beginning ofRun Period 4, olefin conversion was 98.8% and at 942 run hours theolefin conversion was 98.4%. The run was stopped after 942 hourson-stream but could have continued longer.

Alkylated aromatic hydrocarbon products containing excess benzene werecollected during the course of the run. After distillation to removeexcess aromatic hydrocarbon, analysis showed that greater than 97%conversion of olefin was achieved during most of the course of the run.

Example 7 Preparation of Alkylbenzene Sulfonic Acids

A mixture of 85 weight % of the alkylated benzene prepared using thezeolite Y catalyst and 15 weight % of the alkylated benzene preparedusing mordenite zeolite catalyst as in Examples 5 and 6 above wassulfonated by a concurrent stream of sulfur trioxide (SO₃) and air within a tubular reactor (2 meters long, 1 centimeter inside diameter) in adown flow mode using the following conditions:

Reactor temperature was 60° C., SO₃ flow rate was 73 grams per hour, andalkylate flow rate was 327 grams per hour at a SO₃ to alkylate molarratio of 1.05. The SO₃ was generated by passing a mixture of oxygen andsulfur dioxide (SO₂) through a catalytic furnace containing vanadiumoxide (V₂O₅). The resulting crude alkylbenzene sulfonic acid had thefollowing properties based on the total weight of the product: weight %of HSO₃ was 15.61% and weight % of H₂SO₄ was 0.53.

The crude alkylbenzene sulfonic acid (1665 grams) was diluted with 83grams of 100 Neutral diluent oil and placed in a 4 liter four-neck glassreactor fitted with a stainless steel mechanical agitator rotating atabout 300 rpm, a condenser and a gas inlet tube (2 millimeters insidediameter) located just above the agitator blades for the introduction ofnitrogen. The contents of the reactor were placed under vacuum (40millimeters Hg) and the reactor was heated to 110° C. with stirring andnitrogen was bubbled through the mixture at about 30 liters per hour forabout 30 minutes until the weight % of H₂SO₄ is less than about 0.3weight %. This material is the final alkylbenzene sulfonic acid.

The final alkylbenzene sulfonic acid had the following properties basedon the total weight of the product: weight % of HSO₃ was 14.95 andweight % of H₂SO₄ was 0.17.

Example 7 Preparation of Alkylbenzene Sulfonates

To a 5 liter four-neck glass reactor equipped with heating and coolingcapability and fitted with a stainless steel mechanical agitatorrotating at between 300 and 350 rpm, a gas inlet tube (2 millimetersinside diameter) located just above the agitator blades for the additionof CO₂, a distillation column and condenser under nitrogen gas wascharged 129.4 grams of centrate.

The centrate was a mixture of the sludge fractions previously producedduring the purification of high TBN carbonated, overbased syntheticsulfonates by centrifugation and decantation and was added to thereaction mixture of this example for recycling the contents of thecentrate. The centrate had a TBN of 197 and contained approximately 73grams of xylene solvent, 12 grams active calcium sulfonate, 9 gramscalcium hydroxide and calcium carbonate, 8 grams of carbon dioxide, and23 grams of 100 Neutral diluent oil. Next, 40 grams of methanol, 207grams of xylene solvent, 296.5 grams (0.59 mole) of the alkylbenzenesulfonic acid (HSO₃ was 14.95 weight % based on the total weight of thereaction mixture) from Example 6 above was charged to the reactor over15 minutes at room temperature. A slurry of 160 grams (2.16 mole) ofcalcium hydroxide, 362 grams of xylene solvent and 94.2 grams ofmethanol was added to the reactor and the contents of the reactor werecooled to 25° C. Subsequently, 33 grams (0.79 mole) of CO₂ was added tothe reactor through the gas inlet tube over 39 minutes while thetemperature of the reactor increased to about 32° C. A second slurrycomposed of 160 grams (2.16 mole) of calcium hydroxide, 384 grams xylenesolvent, and 131 grams of methanol was then added to the reactorconcurrently with 0.9 grams of CO₂ over about 1 minute. Then 92 grams ofCO₂ was added to the reactor over 64 minutes while the temperature ofthe reactor was increased from about 30° C. to about 41° C. A thirdslurry composed of 82 grams of oxide and 298 grams of xylene solvent wasthen charged to the reactor concurrently with 1.4 grams of CO₂ overabout 1 minute. Next, 55 grams (1.25 mole) of CO₂ was added to thereactor over approximately 60 minutes while keeping the reactortemperature at approximately 38° C.

The water and methanol were then distilled from the reactor by firstheating the reactor to 65° C. over about 40 minutes at atmosphericpressure and then to 93° C. over about 60 minutes at atmosphericpressure and then finally to 130° C. over about 30 minutes atatmospheric pressure. The temperature of the reactor was then decreasedto 110° C. over about 60 minutes at atmospheric pressure and next thencooled to approximately 30° C. and 475.7 grams of 600 Neutral diluentoil was added to the reactor followed by 413 grams of xylene solvent.The sediment in the product was then removed by centrifugation. Thexylene solvent in the product was distilled by heating the product to204° C. over approximately 45 minutes at 30 millimeters Hg vacuum andholding the product at 204° C. and 30 millimeters Hg vacuum for 10minutes. The vacuum was replaced with nitrogen gas and the contentsallowed to cool to room temperature to obtain the overbased sulfonatehaving the following properties based on the total weight of theproduct:

The weight % of calcium was 16.2, TBN was 429, weight % of sulfur was1.70, weight % of calcium sulfonate was 0.94, and viscosity was 111 cStat 100° C.

1. A process for preparing an alkylated aromatic composition comprising:(a) contacting at least one aromatic hydrocarbon with at least oneolefin under alkylation conditions in the presence of a zeolite catalysthaving a macropore structure comprising zeolite Y, and wherein the peakmacropore diameter of the catalyst, measured by ASTM Test No. D 4284-03,is less than or equal to about 2000 angstroms and the cumulative porevolume of be catalyst at pore diameters less than or equal to about 500angstroms, measured by ASTM Test No. D 4284-03, is less than or equal toabout 0.30 milliliters per gram to form a first alkylated aromatichydrocarbon product; (b) contacting at least one aromatic hydrocarbonwith at least one olefin under alkylation conditions in the presence ofa zeolite catalyst having a macropore structure comprising mordenitezeolite having a silica to alumina molar ratio of about 50:1 to about105:1, and wherein the peak macropore diameter of the catalyst, measuredby ASTM Test No. D 4284-03, is less than or equal to about 900 angstromsand the cumulative pore volume of the catalyst at pore diameters lessthan or equal to about 500 angstroms, measured by ASTM Test No. D4284-03, is less than or equal to about 0.30 milliliters per gram toform a second alkylated aromatic hydrocarbon product; and (c) combiningthe first alkylated aromatic hydrocarbon product and the secondalkylated aromatic hydrocarbon product to form the alkylated aromaticcomposition; wherein steps (a) and (b) can be conducted in any order. 2.The process of claim 1 wherein step (b) further comprises thereactivation of the deactivated zeolite catalyst with an aromatichydrocarbon flush.
 3. The process of claim 1 further comprisingsulfonating the alkylated aromatic composition to form an alkylatedaromatic sulfonic acid.
 4. The process of claim 3 further comprisingreacting the alkylated aromatic sulfonic acid with an alkaline earthmetal and carbon dioxide to produce a carbonated overbased alkylatedaromatic sulfonate.
 5. The process of claim 1 wherein the firstalkylated aromatic hydrocarbon product in the alkylated aromaticcomposition is in the range of about 40 percent to about 99 percentbased on the total alkylated aromatic composition.
 6. The process ofclaim 5 wherein the first alkylated aromatic hydrocarbon product in thealkylated aromatic composition is in the range of about 50 percent toabout 90 percent based on the total alkylated aromatic composition. 7.The process of claim 6 wherein the first alkylated aromatic hydrocarbonproduct in the alkylated aromatic composition is in the range of about70 percent to about 80 percent based on the total alkylated aromaticcomposition.
 8. The process of claim 1 wherein the olefin in step (a)and step (b) is independently an alpha olefin, an isomerized olefin, abranched-chain olefin, or mixtures thereof.
 9. The process of claim 8wherein the alpha olefin or isomerized olefin has from about 6 carbonatoms to about 40 carbon atoms.
 10. The process of claim 9 wherein thealpha olefin or isomerized olefin has from about 20 carbon atoms toabout 40 carbon atoms.
 11. The process of claim 8 wherein thebranched-chain olefin has from about 6 carbon atoms to about 70 carbonatoms.
 12. The process of claim 11 wherein the branched-chain olefin hasfrom about 8 carbon atoms to about 50 carbon atoms.
 13. The process ofclaim 12 wherein the branched-chain olefin has from about 12 carbonatoms to about 18 carbon atoms.
 14. The process of claim 1 wherein theolefin in step (a) or step (b) is independently apartially-branched-chain isomerized olefin, and wherein the olefin hasfrom about 6 carbon atoms to about 40 carbon atoms.
 15. The process ofclaim 14 wherein the partially-branched-chain isomerized olefin has fromabout 20 carbon atoms to about 40 carbon atoms.
 16. The process of claim1 wherein the aromatic hydrocarbon in step (a) and step (b) isindependently toluene or benzene.
 17. The process of claim 1 wherein thecumulative pore volume of the zeolite catalysts at pore diameters lessthan or equal to about 400 angstroms in steps (a) and (b) are less thanor equal to about 0.30 milliliters per gram.
 18. The process of claim 17wherein the cumulative pore volume of the zeolite catalysts at porediameters less than or equal to about 300 angstroms in steps (a) and (b)are less than or equal to about 0.25 milliliters per gram.
 19. Theprocess of claim 18 wherein the cumulative pore volume of the zeolitecatalysts at pore diameters less than or equal to about 300 angstroms insteps (a) and (b) are lees than or equal to about 0.20 milliliters pergram.
 20. The process of claim 19 wherein the cumulative pore volume ofthe zeolite catalysts at pore diameters lees than or equal to about 400angstroms in steps (a) and (b) are in the range of about 0.05milliliters per gram to about 0.18 milliliters per gram.
 21. The processof claim 20 wherein the cumulative pore volume of the zeolite catalystsat pore diameters less thin or equal to about 300 angstroms in steps (a)and (b) are In the range of about 0.08 milliliters per gram to about0.16 milliliters per gram.
 22. The process of claim 1 wherein in step(a) the peak macropore diameter of the zeolite Y catalyst is in therange of about 700 angstroms to about 1800 angstroms.
 23. The process ofclaim 22 wherein in step (a) the peak macropore diameter of the moltscatalyst is in the range of about 750 angstroms to about 1600 angstroms.24. The process of claim 23 wherein in step (a) the peak macroporediameter of the zeolite catalyst is in the range of about 800 angstromsto about 1400 angstroms.
 25. The process of claim 1 wherein in step (b)the peak macropore diameter of the mordenite zeolite catalyst is in therange of about 400 angstroms to about 800 angstroms.
 26. The process ofclaim 25 wherein in step (b) the peak macropore diameter of themordenite zeolite catalyst is in the range of about 400 angstroms toabout 700 angstroms.
 27. The process of claim 26 wherein m step (b) thepeak macropore diameter of the mordenite zeolite catalyst is in therange of about 450 angstroms to about 600 angstroms.
 28. The process ofclaim 1 wherein in step (a) the zeolite Y catalyst has a silica toalumina ratio of about 5:1 to about 100:1.
 29. The process of claim 28wherein in step (a) the zeolite Y catalyst has a silica to alumina ratioof about 30:1 to about 90:1.
 30. The process of claim 29 wherein in step(a) the zeolite Y catalyst has a silica to alumina ratio of about 60:1to about 80:1.
 31. The process of claim 1 wherein in step (b) themordenite zeolite catalyst has a silica to alumina ratio of about 60:1to about 80:1.
 32. The process of claim 1 wherein the zeolite Y in step(a) and the mordenite zeolite in step (b) contain a binder.
 33. Theprocess of claim 32 wherein the binder in the zeolite Y in step (a) andthe binder in the mordenite zeolite in step (b) is alumina.
 34. Theprocess of claim 1 wherein the zeolite Y in step (a) and the mordenitezeolite in step (b) are in the form of a tablet.